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A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals

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A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals data Data Descriptor A Data Resource for Sulfuric Acid Reactivity of Organic Chemicals William Bains 1,* , Janusz Jurand Petkowski 1 and Sara Seager 1,2,3 1 Department of Earth, Atmospheric and Planetary Sciences, Massachusetts Institute of Technology, 77 Massachusetts. Avenue., Cambridge, MA 02139, USA; [email protected] (J.J.P.); [email protected] (S.S.) 2 Department of Physics, Massachusetts Institute of Technology, 77 Massachusetts. Avenue., Cambridge, MA 02139, USA 3 Department of Aeronautics and Astronautics, Massachusetts Institute of Technology, 77 Massachusetts. Avenue., Cambridge, MA 02139, USA * Correspondence: [email protected] Abstract: We describe a dataset of the quantitative reactivity of organic chemicals with concentrated sulfuric acid. As well as being a key industrial chemical, sulfuric acid is of environmental and planetary importance. In the absence of measured reaction kinetics, the reaction rate of a chemical with sulfuric acid can be estimated from the reaction rate of structurally related chemicals. To allow an approximate prediction, we have collected 589 sets of kinetic data on the reaction of organic chemicals with sulfuric acid from 262 literature sources and used a functional group-based approach to build a model of how the functional groups would react in any sulfuric acid concentration from 60–100%, and between −20 ◦C and 100 ◦C. The data set provides the original reference data and kinetic measurements, parameters, intermediate computation steps, and a set of first-order rate constants for the functional groups across the range of conditions −20 ◦C–100 ◦C and 60–100% sulfuric acid. The dataset will be useful for a range of studies in chemistry and atmospheric sciences where the reaction rate of a chemical with sulfuric acid is needed but has not been measured. Citation: Bains, W.; Petkowski, J.J.; Seager, S. A Data Resource for Dataset: doi: 10.5281/zenodo.4467868 Sulfuric Acid Reactivity of Organic Chemicals. Data 2021, 6, 24. https://doi.org/10.3390/ Dataset License: Dataset is made available under the Creative Commons license CC BY (SA). data6030024 Keywords: kinetics; reactivity; sulfuric acid; sulfonation; solvolysis Academic Editor: Igor I. Baskin Received: 4 December 2020 Accepted: 22 February 2021 1. Summary Published: 25 February 2021 The chemistry of sulfuric acid is of practical importance to industry [1], as well as to atmospheric sciences and astronomy. The kinetics of reaction with sulfuric acid—whether Publisher’s Note: MDPI stays neutral a substance will react and how fast, under a wide range of conditions—is, therefore, of with regard to jurisdictional claims in great practical importance. The reactivity of a molecule in sulfuric acid may be calculated published maps and institutional affil- exactly when the molecule’s pKa is known (and so its ionization state in the acid of iations. different concentrations is known), and the reaction mechanism is known (reviewed in [1–4]). However, these properties are rarely known unless the kinetics have already been experimentally measured for the compound of interest or a compound that is structurally closely related. Estimating the stability of new substances in sulfuric acid, therefore, must Copyright: © 2021 by the authors. rely on comparison with diverse chemicals containing functional groups similar to the test Licensee MDPI, Basel, Switzerland. molecule. The dataset presented in this paper provides a set of kinetic examples for such This article is an open access article reactivity estimation and modeling from literature data and an extrapolated set of kinetic distributed under the terms and parameters based on the experimentally derived examples. conditions of the Creative Commons Data on the reactivity of chemicals in sulfuric acid is scattered in diverse literature, Attribution (CC BY) license (https:// using diverse reporting methods and units. We compiled data on the reaction kinetics for creativecommons.org/licenses/by/ 589 reactions in concentrated sulfuric acid from 262 literature sources and converted them 4.0/). Data 2021, 6, 24. https://doi.org/10.3390/data6030024 https://www.mdpi.com/journal/data Data 2021, 6, x FOR PEER REVIEW 2 of 10 Data on the reactivity of chemicals in sulfuric acid is scattered in diverse literature, Data 2021, 6, 24 2 of 10 using diverse reporting methods and units. We compiled data on the reaction kinetics for 589 reactions in concentrated sulfuric acid from 262 literature sources and converted them to a dataset in a unified system of units. Literature searches were both from cita- tions toin abooks dataset and in apapers unified on system sulfuric of units.acid chemistry Literature and searches by keyword. were both In fromthe case citations of in phosphine,books anda model papers of reactivity on sulfuric was acid built chemistry from scattered and by keyword.literature hints In the to case fill ofin phosphine,a cru- cial parta model of chemical of reactivity space, was for builtreasons from de scatteredscribed below. literature The hintscompiled to fill data in a were crucial then part of used chemicalto build space,a dataset for of reasons extrapolated described reacti below.on rates The compiledfor a set dataof 130 were functional then used groups to build a liabledataset to breakdown of extrapolated or solvolysis reaction in ratesconcen fortrated a set ofsulfuric 130 functional acid and groups a complementary liable to breakdown set of reactionor solvolysis parameters in concentrated for sulfonation sulfuric of phenyl acid and rings. a complementary set of reaction parameters Thefor sulfonationdata provided of phenyl by the rings.dataset can be used to give a pragmatically based indica- tion of theThe stability data providedof an arbitrary by the chemical dataset can in sulfuric be used toacid. give Detailed a pragmatically mechanistic based studies indication (eitherof ab the initio stability quantum of an arbitrarycalculations chemical of reaction in sulfuric paths acid. or Detaileddetailed mechanisticexperimental studies kinetic (either studies)ab initiowouldquantum give much calculations more accurate of reaction predictions paths orbut detailed are extremely experimental time-consuming. kinetic studies) In theirwould absence, give we much believe more that accurate the dataset predictions presented but arein this extremely paper will time-consuming. be useful for any In their absence, we believe that the dataset presented in this paper will be useful for any researcher researcher looking to explore the reactivity of chemicals in sulfuric acid for applications looking to explore the reactivity of chemicals in sulfuric acid for applications such as, but such as, but not limited to, stratospheric chemistry or planetary atmospheric modeling. not limited to, stratospheric chemistry or planetary atmospheric modeling. The dataset The dataset will also have industrial applications, where sulfuric acid is a widely used will also have industrial applications, where sulfuric acid is a widely used reagent. In this reagent. In this regard, future work could extend this study to the reactivity of organic regard, future work could extend this study to the reactivity of organic compounds with compounds with nitric acid and with nitric and sulfuric acid mixtures, which are widely nitric acid and with nitric and sulfuric acid mixtures, which are widely used in nitration used in nitration reactions [5]. reactions [5]. 2. Data2. DataDescription Description 2.1. Summary2.1. Summary of Data of Data The datasetThe dataset is a iscompilation a compilation of literature of literature data data on on sulfuric sulfuric acid acid reactivity reactivity of of mole- molecules, cules,converted converted to to unified unified data data units. units. The The data data fall fall into into three three parts: parts: • Original• Original literature literature data data(Excel (Excel Sheets Sheets “Data “Data”” and “References”); and “References”); • Functional• Functional group group definitions definitions (Excel (Excel Sheet Sheet “Groups “Groups List”) List”); ; • Derived• Derived kinetic kinetic constants constants (Excel (Excel Sheets Sheets “Concentration “Concentration Lookup”, Lookup”, “Group “Group defaults” defaults” and “Groupand “Group Rates Rates Matrix”). Matrix”). The derivedThe derived kinetic kinetic constants constants are extrapolated are extrapolated from fromthe literature the literature data datausing using the the functionalfunctional group group definitions, definitions, as described as described below below in Section in Section 3.5. 3.5. The structureThe structure of the of data the datais illustrated is illustrated in Figure in Figure 1. 1. FigureFigure 1. Data 1. typesData and types their and relationships their relationships are presen areted presented in this paper. in this Top paper. row—the Top row—the data sets data sets presentedpresented here. Central here. Central row—the row—the relationship relationship between between the data thesets dataand their sets andinterconversion. their interconversion. BottomBottom row—types row—types of data of and data applications and applications that can that be can taken be takenfrom the from current the current data set data for set uses for as uses a as a literatureliterature resource, resource, a resource a resource for modeling for modeling or a lookup or a lookup table tablefor chemical for chemical stability. stability. Data 2021, 6, 24 3 of 10 Chemical Structure Format (the SMILES Convention) Throughout, we have used the simplified molecular-input line-entry
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